Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025007/zl2032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025007/zl2032Isup2.hkl |
CCDC reference: 651523
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.006 Å
- R factor = 0.042
- wR factor = 0.116
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 600 Deg. PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.93 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.29 Ratio PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.37 PLAT431_ALERT_2_C Short Inter HL..A Contact Br3 .. N2 .. 3.20 Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact Br4 .. N4 .. 3.27 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature on the crystal structures of some other brominated Tröger's base analogues, see: Hansson et al. (2003); Bhuiyan et al. (2006); Lenev et al. (2006); Faroughi et al. (2006a,b, 2007).
For related literature, see: Hof et al. (2005); Jensen & Wärnmark (2001); Jensen, Strozyk & Wärnmark (2002); Jensen, Tejler & Wärnmark (2002); Kiehne & Lützen (2004); Solano et al. (2005).
The title compound was prepared on a 2 g scale according to the literature procedure (Hansson et al., 2003) in an almost quantitative yield. Single crystals of (I) were produced by slow evaporation of a dichloromethane solution.
H atoms were positioned geometrically, with C—H = 0.95, 0.99 and 0.98 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms. The methyl groups were free to rotate about their respective C—C bonds in the refinement.
The halogen substituents on Tröger's base analogues have been successfully converted into a range of other functionalities via exchange reactions (Jensen & Wärnmark, 2001; Jensen, Strozyk & Wärnmark, 2002; Jensen et al., 2002; Kiehne & Lützen, 2004; Hof et al., 2005). An important feature of this family of molecules is the methano-strapped diazocine bridge that creates the cavity present in these compounds. The bridge also imparts a twist within the compounds such that the two aryl rings are offset with respect to one another. The dihedral angle between these rings has been measured across a range of compounds to lie between 82° (Solano et al., 2005) and 108° (Faroughi et al., 2006b) for simple dibenzo Tröger's base analogues, and is dependant upon the nature of the substituents on the aromatic rings. We were interested in preparing a range of dihalo Tröger's base analogues as precursors for supramolecular recognition elements. The synthesis of (I) in racemic form was achieved by reacting 2-bromo-4-methylaniline with paraformaldehyde in trifluoroacetic acid (TFA) as shown in Fig. 2. The molecular structure of (I) is shown in Fig. 1.
For related literature on the crystal structures of some other brominated Tröger's base analogues, see: Hansson et al. (2003); Bhuiyan et al. (2006); Lenev et al. (2006); Faroughi et al. (2006a,b, 2007).
For related literature, see: Hof et al. (2005); Jensen & Wärnmark (2001); Jensen, Strozyk & Wärnmark (2002); Jensen, Tejler & Wärnmark (2002); Kiehne & Lützen (2004); Solano et al. (2005).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN for Windows (Molecular Structure Corporation, 1998), Xtal3.6 (Hall et al., 1999), ORTEPII (Johnson, 1976) and WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX.
Fig. 1. Molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level. | |
Fig. 2. Preparation of the title compound. |
C17H16Br2N2 | Z = 4 |
Mr = 408.14 | F(000) = 808 |
Triclinic, P1 | Dx = 1.723 Mg m−3 |
Hall symbol: -P 1 | Melting point: 465 K |
a = 10.169 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.477 (5) Å | Cell parameters from 993 reflections |
c = 15.269 (6) Å | θ = 2–27° |
α = 104.259 (6)° | µ = 5.15 mm−1 |
β = 106.185 (6)° | T = 150 K |
γ = 103.093 (6)° | Blade, colourless |
V = 1573.1 (11) Å3 | 0.35 × 0.16 × 0.05 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 7031 independent reflections |
Radiation source: fine-focus sealed tube | 5002 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω scans | θmax = 28.2°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→12 |
Tmin = 0.351, Tmax = 0.783 | k = −14→14 |
15349 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0675P)2] where P = (Fo2 + 2Fc2)/3 |
7031 reflections | (Δ/σ)max = 0.001 |
383 parameters | Δρmax = 1.35 e Å−3 |
0 restraints | Δρmin = −1.13 e Å−3 |
C17H16Br2N2 | γ = 103.093 (6)° |
Mr = 408.14 | V = 1573.1 (11) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.169 (4) Å | Mo Kα radiation |
b = 11.477 (5) Å | µ = 5.15 mm−1 |
c = 15.269 (6) Å | T = 150 K |
α = 104.259 (6)° | 0.35 × 0.16 × 0.05 mm |
β = 106.185 (6)° |
Bruker SMART 1000 CCD area-detector diffractometer | 7031 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5002 reflections with I > 2σ(I) |
Tmin = 0.351, Tmax = 0.783 | Rint = 0.036 |
15349 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.01 | Δρmax = 1.35 e Å−3 |
7031 reflections | Δρmin = −1.13 e Å−3 |
383 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.57686 (5) | 0.30388 (5) | −0.01862 (3) | 0.03267 (13) | |
Br2 | 0.94459 (5) | 0.21585 (5) | 0.50648 (3) | 0.03313 (13) | |
N1 | 0.6106 (3) | 0.2665 (3) | 0.1804 (2) | 0.0207 (7) | |
N2 | 0.7408 (3) | 0.2825 (3) | 0.3459 (2) | 0.0189 (7) | |
C1 | 0.7347 (4) | 0.3580 (4) | 0.1821 (3) | 0.0196 (8) | |
C2 | 0.7393 (4) | 0.3851 (4) | 0.0987 (3) | 0.0222 (9) | |
C3 | 0.8574 (4) | 0.4732 (4) | 0.0979 (3) | 0.0253 (9) | |
H3 | 0.8576 | 0.4883 | 0.0395 | 0.030* | |
C4 | 0.9755 (4) | 0.5392 (4) | 0.1832 (3) | 0.0254 (9) | |
C5 | 0.9709 (4) | 0.5158 (4) | 0.2672 (3) | 0.0218 (9) | |
H5 | 1.0498 | 0.5626 | 0.3259 | 0.026* | |
C6 | 0.8530 (4) | 0.4249 (4) | 0.2682 (3) | 0.0180 (8) | |
C7 | 0.8571 (4) | 0.3987 (4) | 0.3617 (3) | 0.0207 (9) | |
H7A | 0.9519 | 0.3895 | 0.3925 | 0.025* | |
H7B | 0.8472 | 0.4721 | 0.4065 | 0.025* | |
C8 | 0.7727 (4) | 0.1687 (4) | 0.3088 (3) | 0.0211 (9) | |
C9 | 0.8670 (4) | 0.1269 (4) | 0.3707 (3) | 0.0234 (9) | |
C10 | 0.9076 (4) | 0.0219 (4) | 0.3362 (3) | 0.0283 (10) | |
H10 | 0.9739 | −0.0024 | 0.3798 | 0.034* | |
C11 | 0.8519 (4) | −0.0473 (4) | 0.2384 (3) | 0.0277 (10) | |
C12 | 0.7502 (4) | −0.0115 (4) | 0.1770 (3) | 0.0261 (10) | |
H12 | 0.7061 | −0.0615 | 0.1106 | 0.031* | |
C13 | 0.7119 (4) | 0.0953 (4) | 0.2106 (3) | 0.0219 (9) | |
C14 | 0.6071 (4) | 0.1347 (4) | 0.1393 (3) | 0.0229 (9) | |
H14A | 0.6321 | 0.1259 | 0.0803 | 0.027* | |
H14B | 0.5079 | 0.0769 | 0.1203 | 0.027* | |
C15 | 0.6070 (4) | 0.2845 (4) | 0.2783 (3) | 0.0208 (9) | |
H15A | 0.5915 | 0.3667 | 0.3028 | 0.025* | |
H15B | 0.5245 | 0.2166 | 0.2755 | 0.025* | |
C16 | 1.1084 (4) | 0.6328 (4) | 0.1831 (4) | 0.0338 (11) | |
H16A | 1.1496 | 0.7042 | 0.2438 | 0.051* | |
H16B | 1.0807 | 0.6641 | 0.1287 | 0.051* | |
H16C | 1.1803 | 0.5903 | 0.1767 | 0.051* | |
C17 | 0.9049 (5) | −0.1547 (4) | 0.1984 (4) | 0.0402 (13) | |
H17A | 0.8292 | −0.2154 | 0.1388 | 0.060* | |
H17B | 0.9284 | −0.1975 | 0.2461 | 0.060* | |
H17C | 0.9914 | −0.1206 | 0.1845 | 0.060* | |
Br3 | 0.34713 (4) | 0.59722 (4) | 0.47521 (3) | 0.02297 (12) | |
Br4 | 0.16448 (4) | −0.06142 (4) | 0.02942 (3) | 0.02554 (12) | |
N3 | 0.1800 (3) | 0.3402 (3) | 0.3097 (2) | 0.0164 (7) | |
N4 | 0.1316 (3) | 0.1725 (3) | 0.1605 (2) | 0.0177 (7) | |
C18 | 0.2907 (4) | 0.4193 (4) | 0.2894 (3) | 0.0158 (8) | |
C19 | 0.3825 (4) | 0.5349 (4) | 0.3593 (3) | 0.0181 (8) | |
C20 | 0.4944 (4) | 0.6110 (4) | 0.3433 (3) | 0.0211 (9) | |
H20 | 0.5574 | 0.6877 | 0.3928 | 0.025* | |
C21 | 0.5151 (4) | 0.5760 (4) | 0.2554 (3) | 0.0224 (9) | |
C22 | 0.4201 (4) | 0.4640 (4) | 0.1838 (3) | 0.0202 (9) | |
H22 | 0.4299 | 0.4413 | 0.1223 | 0.024* | |
C23 | 0.3105 (4) | 0.3842 (4) | 0.2005 (3) | 0.0172 (8) | |
C24 | 0.2160 (4) | 0.2581 (4) | 0.1228 (3) | 0.0189 (8) | |
H24A | 0.1487 | 0.2739 | 0.0696 | 0.023* | |
H24B | 0.2778 | 0.2159 | 0.0961 | 0.023* | |
C25 | 0.2166 (4) | 0.1128 (4) | 0.2146 (3) | 0.0176 (8) | |
C26 | 0.2474 (4) | 0.0074 (4) | 0.1661 (3) | 0.0182 (8) | |
C27 | 0.3334 (4) | −0.0503 (4) | 0.2159 (3) | 0.0242 (9) | |
H27 | 0.3553 | −0.1197 | 0.1814 | 0.029* | |
C28 | 0.3875 (4) | −0.0067 (4) | 0.3162 (3) | 0.0260 (9) | |
C29 | 0.3515 (4) | 0.0942 (4) | 0.3655 (3) | 0.0237 (9) | |
H29 | 0.3841 | 0.1215 | 0.4341 | 0.028* | |
C30 | 0.2689 (4) | 0.1554 (4) | 0.3161 (3) | 0.0180 (8) | |
C31 | 0.2386 (4) | 0.2689 (4) | 0.3711 (3) | 0.0174 (8) | |
H31A | 0.1687 | 0.2398 | 0.4013 | 0.021* | |
H31B | 0.3292 | 0.3265 | 0.4236 | 0.021* | |
C32 | 0.0695 (4) | 0.2478 (4) | 0.2201 (3) | 0.0184 (8) | |
H32A | 0.0175 | 0.2930 | 0.1826 | 0.022* | |
H32B | −0.0013 | 0.1902 | 0.2363 | 0.022* | |
C33 | 0.6416 (4) | 0.6569 (4) | 0.2401 (3) | 0.0271 (10) | |
H33A | 0.6500 | 0.6117 | 0.1796 | 0.041* | |
H33B | 0.7306 | 0.6743 | 0.2941 | 0.041* | |
H33C | 0.6257 | 0.7371 | 0.2369 | 0.041* | |
C34 | 0.4842 (6) | −0.0687 (5) | 0.3711 (3) | 0.0461 (14) | |
H34A | 0.5715 | −0.0031 | 0.4197 | 0.069* | |
H34B | 0.5112 | −0.1267 | 0.3257 | 0.069* | |
H34C | 0.4321 | −0.1161 | 0.4031 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0257 (2) | 0.0465 (3) | 0.0218 (2) | 0.0129 (2) | 0.00442 (19) | 0.0076 (2) |
Br2 | 0.0322 (3) | 0.0439 (3) | 0.0291 (3) | 0.0202 (2) | 0.0104 (2) | 0.0149 (2) |
N1 | 0.0111 (15) | 0.0274 (19) | 0.0235 (18) | 0.0066 (14) | 0.0089 (14) | 0.0047 (15) |
N2 | 0.0121 (15) | 0.0241 (18) | 0.0218 (18) | 0.0095 (14) | 0.0067 (14) | 0.0055 (14) |
C1 | 0.0152 (18) | 0.022 (2) | 0.023 (2) | 0.0102 (16) | 0.0077 (17) | 0.0060 (17) |
C2 | 0.0156 (19) | 0.029 (2) | 0.022 (2) | 0.0126 (17) | 0.0053 (17) | 0.0056 (18) |
C3 | 0.027 (2) | 0.031 (2) | 0.029 (2) | 0.0175 (19) | 0.0166 (19) | 0.0135 (19) |
C4 | 0.024 (2) | 0.025 (2) | 0.040 (3) | 0.0138 (18) | 0.020 (2) | 0.016 (2) |
C5 | 0.0170 (19) | 0.019 (2) | 0.029 (2) | 0.0110 (16) | 0.0064 (17) | 0.0047 (18) |
C6 | 0.0142 (18) | 0.020 (2) | 0.021 (2) | 0.0118 (16) | 0.0062 (16) | 0.0042 (16) |
C7 | 0.0123 (18) | 0.024 (2) | 0.024 (2) | 0.0069 (16) | 0.0044 (16) | 0.0060 (17) |
C8 | 0.0137 (18) | 0.023 (2) | 0.029 (2) | 0.0059 (16) | 0.0118 (17) | 0.0067 (18) |
C9 | 0.0162 (19) | 0.026 (2) | 0.031 (2) | 0.0067 (17) | 0.0118 (18) | 0.0094 (18) |
C10 | 0.018 (2) | 0.030 (2) | 0.048 (3) | 0.0116 (18) | 0.019 (2) | 0.020 (2) |
C11 | 0.017 (2) | 0.016 (2) | 0.054 (3) | 0.0035 (17) | 0.021 (2) | 0.010 (2) |
C12 | 0.021 (2) | 0.019 (2) | 0.034 (2) | 0.0012 (17) | 0.0157 (19) | −0.0001 (18) |
C13 | 0.0135 (18) | 0.020 (2) | 0.034 (2) | 0.0027 (16) | 0.0155 (18) | 0.0062 (18) |
C14 | 0.0112 (18) | 0.026 (2) | 0.027 (2) | 0.0031 (16) | 0.0080 (17) | 0.0013 (18) |
C15 | 0.0128 (18) | 0.027 (2) | 0.025 (2) | 0.0080 (16) | 0.0092 (17) | 0.0080 (18) |
C16 | 0.023 (2) | 0.031 (3) | 0.058 (3) | 0.011 (2) | 0.023 (2) | 0.021 (2) |
C17 | 0.035 (3) | 0.024 (2) | 0.072 (4) | 0.014 (2) | 0.035 (3) | 0.013 (2) |
Br3 | 0.0167 (2) | 0.0248 (2) | 0.0216 (2) | 0.00433 (16) | 0.00694 (16) | −0.00018 (17) |
Br4 | 0.0208 (2) | 0.0270 (2) | 0.0212 (2) | 0.00706 (17) | 0.00518 (17) | −0.00192 (17) |
N3 | 0.0076 (14) | 0.0220 (18) | 0.0175 (17) | 0.0034 (13) | 0.0051 (13) | 0.0036 (14) |
N4 | 0.0100 (14) | 0.0197 (17) | 0.0204 (17) | 0.0054 (13) | 0.0042 (13) | 0.0021 (14) |
C18 | 0.0103 (17) | 0.018 (2) | 0.021 (2) | 0.0081 (15) | 0.0061 (15) | 0.0058 (16) |
C19 | 0.0118 (17) | 0.020 (2) | 0.022 (2) | 0.0077 (15) | 0.0063 (16) | 0.0040 (16) |
C20 | 0.0133 (18) | 0.016 (2) | 0.027 (2) | 0.0018 (16) | 0.0037 (17) | 0.0027 (17) |
C21 | 0.0149 (18) | 0.022 (2) | 0.035 (2) | 0.0079 (16) | 0.0113 (18) | 0.0127 (19) |
C22 | 0.0162 (19) | 0.026 (2) | 0.027 (2) | 0.0132 (17) | 0.0131 (17) | 0.0110 (18) |
C23 | 0.0106 (17) | 0.022 (2) | 0.020 (2) | 0.0086 (15) | 0.0043 (15) | 0.0055 (16) |
C24 | 0.0160 (19) | 0.021 (2) | 0.018 (2) | 0.0063 (16) | 0.0063 (16) | 0.0040 (16) |
C25 | 0.0092 (17) | 0.020 (2) | 0.022 (2) | 0.0024 (15) | 0.0060 (16) | 0.0055 (16) |
C26 | 0.0104 (17) | 0.019 (2) | 0.021 (2) | 0.0011 (15) | 0.0064 (16) | 0.0025 (16) |
C27 | 0.020 (2) | 0.022 (2) | 0.031 (2) | 0.0068 (17) | 0.0122 (18) | 0.0052 (18) |
C28 | 0.025 (2) | 0.025 (2) | 0.030 (2) | 0.0136 (18) | 0.0085 (19) | 0.0092 (19) |
C29 | 0.022 (2) | 0.022 (2) | 0.027 (2) | 0.0080 (17) | 0.0082 (18) | 0.0081 (18) |
C30 | 0.0101 (17) | 0.017 (2) | 0.022 (2) | 0.0010 (15) | 0.0064 (16) | 0.0006 (16) |
C31 | 0.0132 (18) | 0.021 (2) | 0.017 (2) | 0.0040 (15) | 0.0068 (16) | 0.0042 (16) |
C32 | 0.0085 (17) | 0.021 (2) | 0.021 (2) | 0.0040 (15) | 0.0040 (15) | 0.0007 (16) |
C33 | 0.017 (2) | 0.028 (2) | 0.041 (3) | 0.0064 (18) | 0.0155 (19) | 0.014 (2) |
C34 | 0.064 (4) | 0.050 (3) | 0.037 (3) | 0.043 (3) | 0.017 (3) | 0.013 (3) |
Br1—C2 | 1.907 (4) | Br3—C19 | 1.903 (4) |
Br2—C9 | 1.910 (4) | Br4—C26 | 1.896 (4) |
N1—C1 | 1.436 (5) | N3—C18 | 1.434 (5) |
N1—C15 | 1.470 (5) | N3—C32 | 1.465 (4) |
N1—C14 | 1.476 (5) | N3—C31 | 1.481 (5) |
N2—C8 | 1.436 (5) | N4—C25 | 1.431 (5) |
N2—C15 | 1.469 (5) | N4—C32 | 1.467 (4) |
N2—C7 | 1.485 (5) | N4—C24 | 1.484 (5) |
C1—C2 | 1.394 (6) | C18—C19 | 1.399 (5) |
C1—C6 | 1.403 (5) | C18—C23 | 1.402 (5) |
C2—C3 | 1.389 (6) | C19—C20 | 1.388 (5) |
C3—C4 | 1.394 (6) | C20—C21 | 1.393 (5) |
C3—H3 | 0.9500 | C20—H20 | 0.9500 |
C4—C5 | 1.384 (6) | C21—C22 | 1.392 (5) |
C4—C16 | 1.525 (6) | C21—C33 | 1.518 (5) |
C5—C6 | 1.406 (5) | C22—C23 | 1.399 (5) |
C5—H5 | 0.9500 | C22—H22 | 0.9500 |
C6—C7 | 1.521 (5) | C23—C24 | 1.521 (5) |
C7—H7A | 0.9900 | C24—H24A | 0.9900 |
C7—H7B | 0.9900 | C24—H24B | 0.9900 |
C8—C13 | 1.401 (6) | C25—C26 | 1.404 (5) |
C8—C9 | 1.404 (6) | C25—C30 | 1.404 (5) |
C9—C10 | 1.390 (6) | C26—C27 | 1.386 (5) |
C10—C11 | 1.386 (6) | C27—C28 | 1.388 (6) |
C10—H10 | 0.9500 | C27—H27 | 0.9500 |
C11—C12 | 1.400 (6) | C28—C29 | 1.398 (5) |
C11—C17 | 1.515 (6) | C28—C34 | 1.525 (6) |
C12—C13 | 1.392 (5) | C29—C30 | 1.395 (5) |
C12—H12 | 0.9500 | C29—H29 | 0.9500 |
C13—C14 | 1.529 (6) | C30—C31 | 1.511 (5) |
C14—H14A | 0.9900 | C31—H31A | 0.9900 |
C14—H14B | 0.9900 | C31—H31B | 0.9900 |
C15—H15A | 0.9900 | C32—H32A | 0.9900 |
C15—H15B | 0.9900 | C32—H32B | 0.9900 |
C16—H16A | 0.9800 | C33—H33A | 0.9800 |
C16—H16B | 0.9800 | C33—H33B | 0.9800 |
C16—H16C | 0.9800 | C33—H33C | 0.9800 |
C17—H17A | 0.9800 | C34—H34A | 0.9800 |
C17—H17B | 0.9800 | C34—H34B | 0.9800 |
C17—H17C | 0.9800 | C34—H34C | 0.9800 |
C1—N1—C15 | 111.0 (3) | C18—N3—C32 | 110.8 (3) |
C1—N1—C14 | 112.6 (3) | C18—N3—C31 | 111.9 (3) |
C15—N1—C14 | 107.8 (3) | C32—N3—C31 | 107.7 (3) |
C8—N2—C15 | 110.6 (3) | C25—N4—C32 | 110.9 (3) |
C8—N2—C7 | 112.5 (3) | C25—N4—C24 | 112.7 (3) |
C15—N2—C7 | 107.4 (3) | C32—N4—C24 | 107.7 (3) |
C2—C1—C6 | 118.1 (4) | C19—C18—C23 | 118.3 (3) |
C2—C1—N1 | 120.9 (3) | C19—C18—N3 | 120.0 (3) |
C6—C1—N1 | 121.0 (4) | C23—C18—N3 | 121.7 (3) |
C3—C2—C1 | 122.3 (4) | C20—C19—C18 | 121.3 (3) |
C3—C2—Br1 | 117.8 (3) | C20—C19—Br3 | 118.3 (3) |
C1—C2—Br1 | 119.8 (3) | C18—C19—Br3 | 120.2 (3) |
C2—C3—C4 | 119.7 (4) | C19—C20—C21 | 120.6 (4) |
C2—C3—H3 | 120.2 | C19—C20—H20 | 119.7 |
C4—C3—H3 | 120.2 | C21—C20—H20 | 119.7 |
C5—C4—C3 | 118.7 (4) | C22—C21—C20 | 118.5 (4) |
C5—C4—C16 | 120.9 (4) | C22—C21—C33 | 121.3 (4) |
C3—C4—C16 | 120.4 (4) | C20—C21—C33 | 120.2 (4) |
C4—C5—C6 | 121.9 (4) | C21—C22—C23 | 121.3 (4) |
C4—C5—H5 | 119.0 | C21—C22—H22 | 119.3 |
C6—C5—H5 | 119.0 | C23—C22—H22 | 119.3 |
C1—C6—C5 | 119.2 (4) | C22—C23—C18 | 119.9 (4) |
C1—C6—C7 | 121.1 (3) | C22—C23—C24 | 119.6 (3) |
C5—C6—C7 | 119.6 (3) | C18—C23—C24 | 120.4 (3) |
N2—C7—C6 | 112.5 (3) | N4—C24—C23 | 112.3 (3) |
N2—C7—H7A | 109.1 | N4—C24—H24A | 109.1 |
C6—C7—H7A | 109.1 | C23—C24—H24A | 109.1 |
N2—C7—H7B | 109.1 | N4—C24—H24B | 109.1 |
C6—C7—H7B | 109.1 | C23—C24—H24B | 109.1 |
H7A—C7—H7B | 107.8 | H24A—C24—H24B | 107.9 |
C13—C8—C9 | 117.5 (4) | C26—C25—C30 | 118.4 (4) |
C13—C8—N2 | 122.0 (4) | C26—C25—N4 | 119.9 (3) |
C9—C8—N2 | 120.6 (4) | C30—C25—N4 | 121.7 (3) |
C10—C9—C8 | 122.0 (4) | C27—C26—C25 | 121.5 (4) |
C10—C9—Br2 | 118.1 (3) | C27—C26—Br4 | 119.1 (3) |
C8—C9—Br2 | 119.9 (3) | C25—C26—Br4 | 119.4 (3) |
C11—C10—C9 | 120.3 (4) | C26—C27—C28 | 120.1 (4) |
C11—C10—H10 | 119.9 | C26—C27—H27 | 119.9 |
C9—C10—H10 | 119.9 | C28—C27—H27 | 119.9 |
C10—C11—C12 | 118.1 (4) | C27—C28—C29 | 118.9 (4) |
C10—C11—C17 | 120.9 (4) | C27—C28—C34 | 120.1 (4) |
C12—C11—C17 | 120.9 (4) | C29—C28—C34 | 121.0 (4) |
C13—C12—C11 | 121.8 (4) | C30—C29—C28 | 121.4 (4) |
C13—C12—H12 | 119.1 | C30—C29—H29 | 119.3 |
C11—C12—H12 | 119.1 | C28—C29—H29 | 119.3 |
C12—C13—C8 | 120.1 (4) | C29—C30—C25 | 119.6 (4) |
C12—C13—C14 | 119.6 (4) | C29—C30—C31 | 120.3 (3) |
C8—C13—C14 | 120.2 (4) | C25—C30—C31 | 120.1 (4) |
N1—C14—C13 | 112.3 (3) | N3—C31—C30 | 113.2 (3) |
N1—C14—H14A | 109.1 | N3—C31—H31A | 108.9 |
C13—C14—H14A | 109.1 | C30—C31—H31A | 108.9 |
N1—C14—H14B | 109.1 | N3—C31—H31B | 108.9 |
C13—C14—H14B | 109.1 | C30—C31—H31B | 108.9 |
H14A—C14—H14B | 107.9 | H31A—C31—H31B | 107.7 |
N2—C15—N1 | 112.4 (3) | N3—C32—N4 | 112.1 (3) |
N2—C15—H15A | 109.1 | N3—C32—H32A | 109.2 |
N1—C15—H15A | 109.1 | N4—C32—H32A | 109.2 |
N2—C15—H15B | 109.1 | N3—C32—H32B | 109.2 |
N1—C15—H15B | 109.1 | N4—C32—H32B | 109.2 |
H15A—C15—H15B | 107.9 | H32A—C32—H32B | 107.9 |
C4—C16—H16A | 109.5 | C21—C33—H33A | 109.5 |
C4—C16—H16B | 109.5 | C21—C33—H33B | 109.5 |
H16A—C16—H16B | 109.5 | H33A—C33—H33B | 109.5 |
C4—C16—H16C | 109.5 | C21—C33—H33C | 109.5 |
H16A—C16—H16C | 109.5 | H33A—C33—H33C | 109.5 |
H16B—C16—H16C | 109.5 | H33B—C33—H33C | 109.5 |
C11—C17—H17A | 109.5 | C28—C34—H34A | 109.5 |
C11—C17—H17B | 109.5 | C28—C34—H34B | 109.5 |
H17A—C17—H17B | 109.5 | H34A—C34—H34B | 109.5 |
C11—C17—H17C | 109.5 | C28—C34—H34C | 109.5 |
H17A—C17—H17C | 109.5 | H34A—C34—H34C | 109.5 |
H17B—C17—H17C | 109.5 | H34B—C34—H34C | 109.5 |
C15—N1—C1—C2 | −160.4 (4) | C32—N3—C18—C19 | 161.6 (3) |
C14—N1—C1—C2 | 78.6 (4) | C31—N3—C18—C19 | −78.2 (4) |
C15—N1—C1—C6 | 17.9 (5) | C32—N3—C18—C23 | −18.5 (5) |
C14—N1—C1—C6 | −103.0 (4) | C31—N3—C18—C23 | 101.7 (4) |
C6—C1—C2—C3 | 1.5 (6) | C23—C18—C19—C20 | −2.7 (6) |
N1—C1—C2—C3 | 179.9 (3) | N3—C18—C19—C20 | 177.3 (3) |
C6—C1—C2—Br1 | −176.5 (3) | C23—C18—C19—Br3 | 172.6 (3) |
N1—C1—C2—Br1 | 1.9 (5) | N3—C18—C19—Br3 | −7.5 (5) |
C1—C2—C3—C4 | −1.0 (6) | C18—C19—C20—C21 | 2.2 (6) |
Br1—C2—C3—C4 | 176.9 (3) | Br3—C19—C20—C21 | −173.1 (3) |
C2—C3—C4—C5 | −0.7 (6) | C19—C20—C21—C22 | 0.8 (6) |
C2—C3—C4—C16 | 177.8 (4) | C19—C20—C21—C33 | −177.4 (4) |
C3—C4—C5—C6 | 2.1 (6) | C20—C21—C22—C23 | −3.3 (6) |
C16—C4—C5—C6 | −176.5 (4) | C33—C21—C22—C23 | 174.8 (4) |
C2—C1—C6—C5 | −0.1 (5) | C21—C22—C23—C18 | 2.8 (6) |
N1—C1—C6—C5 | −178.5 (3) | C21—C22—C23—C24 | −175.5 (4) |
C2—C1—C6—C7 | −178.8 (3) | C19—C18—C23—C22 | 0.2 (5) |
N1—C1—C6—C7 | 2.8 (5) | N3—C18—C23—C22 | −179.8 (3) |
C4—C5—C6—C1 | −1.6 (6) | C19—C18—C23—C24 | 178.5 (3) |
C4—C5—C6—C7 | 177.1 (4) | N3—C18—C23—C24 | −1.4 (5) |
C8—N2—C7—C6 | 77.8 (4) | C25—N4—C24—C23 | −77.5 (4) |
C15—N2—C7—C6 | −44.1 (4) | C32—N4—C24—C23 | 45.1 (4) |
C1—C6—C7—N2 | 11.2 (5) | C22—C23—C24—N4 | 165.7 (3) |
C5—C6—C7—N2 | −167.5 (3) | C18—C23—C24—N4 | −12.7 (5) |
C15—N2—C8—C13 | 19.4 (5) | C32—N4—C25—C26 | 159.8 (3) |
C7—N2—C8—C13 | −100.8 (4) | C24—N4—C25—C26 | −79.4 (4) |
C15—N2—C8—C9 | −160.6 (3) | C32—N4—C25—C30 | −19.0 (5) |
C7—N2—C8—C9 | 79.3 (4) | C24—N4—C25—C30 | 101.8 (4) |
C13—C8—C9—C10 | 4.4 (6) | C30—C25—C26—C27 | −3.4 (6) |
N2—C8—C9—C10 | −175.6 (4) | N4—C25—C26—C27 | 177.8 (3) |
C13—C8—C9—Br2 | −176.1 (3) | C30—C25—C26—Br4 | 174.6 (3) |
N2—C8—C9—Br2 | 3.9 (5) | N4—C25—C26—Br4 | −4.3 (5) |
C8—C9—C10—C11 | −1.8 (6) | C25—C26—C27—C28 | 2.2 (6) |
Br2—C9—C10—C11 | 178.7 (3) | Br4—C26—C27—C28 | −175.8 (3) |
C9—C10—C11—C12 | −2.6 (6) | C26—C27—C28—C29 | 1.1 (6) |
C9—C10—C11—C17 | 174.5 (4) | C26—C27—C28—C34 | −179.0 (4) |
C10—C11—C12—C13 | 4.3 (6) | C27—C28—C29—C30 | −3.2 (6) |
C17—C11—C12—C13 | −172.8 (4) | C34—C28—C29—C30 | 176.9 (4) |
C11—C12—C13—C8 | −1.7 (6) | C28—C29—C30—C25 | 2.0 (6) |
C11—C12—C13—C14 | 176.3 (3) | C28—C29—C30—C31 | −176.5 (4) |
C9—C8—C13—C12 | −2.7 (6) | C26—C25—C30—C29 | 1.3 (5) |
N2—C8—C13—C12 | 177.4 (3) | N4—C25—C30—C29 | −179.9 (3) |
C9—C8—C13—C14 | 179.4 (3) | C26—C25—C30—C31 | 179.8 (3) |
N2—C8—C13—C14 | −0.5 (6) | N4—C25—C30—C31 | −1.3 (5) |
C1—N1—C14—C13 | 76.9 (4) | C18—N3—C31—C30 | −77.8 (4) |
C15—N1—C14—C13 | −45.8 (4) | C32—N3—C31—C30 | 44.2 (4) |
C12—C13—C14—N1 | −163.5 (3) | C29—C30—C31—N3 | 166.5 (3) |
C8—C13—C14—N1 | 14.5 (5) | C25—C30—C31—N3 | −12.0 (5) |
C8—N2—C15—N1 | −54.2 (4) | C18—N3—C32—N4 | 54.5 (4) |
C7—N2—C15—N1 | 68.9 (4) | C31—N3—C32—N4 | −68.2 (4) |
C1—N1—C15—N2 | −54.8 (4) | C25—N4—C32—N3 | 54.7 (4) |
C14—N1—C15—N2 | 68.9 (4) | C24—N4—C32—N3 | −69.1 (4) |
Experimental details
Crystal data | |
Chemical formula | C17H16Br2N2 |
Mr | 408.14 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 10.169 (4), 11.477 (5), 15.269 (6) |
α, β, γ (°) | 104.259 (6), 106.185 (6), 103.093 (6) |
V (Å3) | 1573.1 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.15 |
Crystal size (mm) | 0.35 × 0.16 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.351, 0.783 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15349, 7031, 5002 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.116, 1.01 |
No. of reflections | 7031 |
No. of parameters | 383 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.35, −1.13 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SAINT, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), TEXSAN for Windows (Molecular Structure Corporation, 1998), Xtal3.6 (Hall et al., 1999), ORTEPII (Johnson, 1976) and WinGX (Farrugia, 1999), WinGX.
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The halogen substituents on Tröger's base analogues have been successfully converted into a range of other functionalities via exchange reactions (Jensen & Wärnmark, 2001; Jensen, Strozyk & Wärnmark, 2002; Jensen et al., 2002; Kiehne & Lützen, 2004; Hof et al., 2005). An important feature of this family of molecules is the methano-strapped diazocine bridge that creates the cavity present in these compounds. The bridge also imparts a twist within the compounds such that the two aryl rings are offset with respect to one another. The dihedral angle between these rings has been measured across a range of compounds to lie between 82° (Solano et al., 2005) and 108° (Faroughi et al., 2006b) for simple dibenzo Tröger's base analogues, and is dependant upon the nature of the substituents on the aromatic rings. We were interested in preparing a range of dihalo Tröger's base analogues as precursors for supramolecular recognition elements. The synthesis of (I) in racemic form was achieved by reacting 2-bromo-4-methylaniline with paraformaldehyde in trifluoroacetic acid (TFA) as shown in Fig. 2. The molecular structure of (I) is shown in Fig. 1.